Monazo dyes of the pyrazolone series



Patented May 7, I929.

UNITED STATES 1,711,639 PATENT OFFICE.

LEON W. GELLER, OF HAMBURG, NEW YORK, ASSIGNOR TO NATIONAL ANILINE &CHEMICAL 00., INCL, OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

MONAZO DYES OF THE PYRAZOIIONE SERIES.

No Drawing.

This invention relates to the production of new monazo dyes of thepyrazolone series which are of value for dyeing 'wool and othermaterial. They also form valuable lakes or pigments. Material dyed orprinted with the new azo dyestufis also constitute a part of the presentinvention.

The new dyestufis may be obtained by coupling the diazo compounds of anorthoaminonaphthol sulfonicacid, more particularly 1.2 and2.1-aminonaphthol sulfonic acids, and especially1.2-aminonaphthol-4-sulfonic acid, and which may contain a nitro-groupsubstituted in the naphthalene nucleus, With the laryl-5-pyrazolones ofthe benzene series which contain a sulfo-group, and may also containhalogen, as a substituent in the aryl nucleus.

The new dyestuffs general formula correspond with the wherein Rsignifies a 1-aryl-5-pyrazolone of the benzene series which contains asulfo In producing the azo dyestuffs of the present invention, onemolecular proportion of the diazo compound of the o-aminonaphtholsulfonic acid is added to a w ell-stirred solution of the pyrazolonesulfonic acid (in slight execess of one molecular proportion) which isrendered and kept slightly alkaline throughout the reaction. Then thecoupling is completed, the mixture is heated to about 40-90 C. and thedyestuif isolated in any suitable manner.

The following specific example will further illustrate the invention,but it is understood that the invention is. not limited thereto. Theparts are by weight.

' E mampZe.-54.5 parts of the sodium salt of the diazo compound ofl-amino-2-hydroxythe silk is-stained very little, if at all.

Application filed October 9, 1925. Serial No. 61,590.

naphthalene-t-sulfonic acid are introduced into a cooled solution of55.5 parts of the sodium salt of 1- (4-sulfophenyl) -3-methyl-5-pyrazolone dissolved in 1000 parts water containing a sufficientquantity of sodium carbonate to maintain an alkaline reaction throughoutthe combination. The mixture is stirred for several hours, and when thecombination is complete, the solution is heated to about 7 0 0., and thedyestuifisolated by acidifying the solution with hydrochloric acid,adding common salt, cooling to about 40 0., and then filtering, pressingand drying in the usual manner. i

The product thus obtained, and Which corresponds with the formula:

is a brownish powder, soluble in water to give an orange solution whichon boiling with zinc dust produces a violet color; and is soluble inconcentrated sulfuric acid toform-a red solu-' tion which on dilutionwith ice changes to an orange. It dyes wool from an acid bathorange-brown shades which onbeing afterchromed yield bluish-red tints ofexcellent fastness to light, washing, fulling and potting. In dyeingwool interwoven with silk, The analogous dyestuff prepared from the1-(2- chlor-4-sulfophenyl) 13-methyl-5-pyrazolone dyes wool similarshades which, when afterchromed, produce somewhat yellower tints of red.

In an analogous manner, dyestufls which show similar properties may beproduced by coupling on the one hand the same or anotherl-sulfoaryl-5-pyrazolone of the benzene series or a halogen derivativethereof, for example, 1 (2.5-'dichlor-3'- sulfophenyl) 5 pyrazolone, 1-(2'.5-dichlor-4-sulfophenyl) -5-pyrazolone, 1-(2.3 -dichlor 6'-sulfophen.yl) -5- pyrazolone, 1- (3'.4'-dichl0r-6-sulfophenyl) 5pyrazolone, 1- (2.3'-dichlor-5- sulfophenyl)- 5 -pyrazolone,1-(3'.4-dichlor-5-sulfophenyl) -5-pyrazolone, 1-(2.4c-dich.lor-5-sulfophenyl) -5-pyrazolone, 1 (3'.6-disulfophe'- nyl.)5-pyrazolone, 1- (2.4-disulfophenyl) -5- pyrazolone, 1- (2'-methyl-5'-sulfophenyl) 5- pyrazolone, 1- (2-methyl-5-sulfophenyl) 5-pyrazolone, 1- (4'-methyl-5' -sulfophenyl) -5- pyrazolone,1-(4'-methyl-6-sulfophenyl)- 5- pyrazolone, 1 (2.4- dimethyl6'-sulfophenyl) -5-pyrazolone, 1- (3'.6-dimethyl-4-sulfophenyl)-5-pyrazolone, 1- (3'-chlor-4-methyl- 6-sulfophenyl) -5-pyrazolone, 1-(3-methyl- 4-chlor-6-sulfophenyl) -5-pyrazolone, 1- (2- methyl-5-chlor-4- sulfophenyl)- 5 pyrazolone, etc., with the diazo compound onthe other hand of the. same or another o-aminonaphthol sulfonic acid ora nitro derivative thereof, for example, the nitrated diazo-compound of1-amino-2-hydroXynaphthalene-lsulfonic acid, or the diazo compound of1.2- aminonapththol-6-sulfonic acid, 1.2-aminonaphthol-3.G disulfonicacid, 2.1-aminonaphthol-fi-sulfonic acid, etc. It will be understoodthat the derivatives of 5-pyrazolone mentioned above carry a methyl or acarboxyl group in the 3-position of the pyrazolone nucleus unlessotherwise specified.

I claim:

1. As a new product, a monazo dyestuti which in the free state containsa grouping which corresponds with the probable formula \COCH-N=NR'wherein R signifies an aryl hydrocarbon radical of the benzene serieswhich contains one or more sulfonic acid groups, and may contain one ortwo halogen atoms, as substituents in the benzene nucleus of the arylradical which is otherwise free from substituents, and R denotes asulfonated naphthalene nucleus which is free from substituents otherthan a single nitro group which may be present and a hydroxyl groupwhich is present and adheres to one of the positions 1 and 2 of thenaphthalene nucleus and the azo bridge adheres to the other of saidpositions.

2. As a new product, a monazo dyestu'fii' which corresponds with theprobable formula (Halogenh:

wherein w=1 or 2; w=0,.1 or 2; y=0, 1 or 2; z=1 or 2; R denotes a methylora carboxyl with} (Halogen): V

wherein w=1 or 2; y=0, 1 or 2; e=0,1 or 2; R denotes a methyl or acarboxyl group; and R signifies a naphthalene nucleus in which thehydroxyl group adheres thereto in one of the two positions 1 and 2 andthe a zo group adheres to the other of said positions.

5. As a new product, a monazo dyestuft which corresponds with theprobable formula (H038): A K

wherein w=1 or 2; l/=0, 1 or 2; z=0,1 or 2; and R denotes a methyl or acarboxyl group.

6. As a new product, a monazo dyestufi which corresponds with theprobable formula wherein 'w=1 or 2; m=0, 1 or 2; y=0 or 1; 2 1 or 2; Rdenotes a methyl or a carboxyl group; and R represents a naphthalenenucleus in which the hydroxyl group is attached to one of the positionsland -2 and the azo bridge is attached to the other of said positions.

7 As a new product, a monazo dystufi.

which corresponds with the probable formula N=on (SOaIDz wherein 00 1 or2; z =0, 1 or 2; 2 1 or 2'; R signifies a methyl or a carboxyl group;and R denotes a naphthalene nuclus in which the hydroXyl group'adherestoone of the two positions 1 and 2 and the azo bridge adheres to theother of said positions.

8. As a new product, a monazo dyestufi' which corresponds with theprobable formula wherein 02 1 or 2; y=0, 1 or 2; and R denotes a methylor a carboxyl group.

9. As a new product, a monazo dyestuff which corresponds with theprobable formula I wherein m=1 or 2 and y=0, 1 or-2.

10. As a new product, a monazo dyestuif which corresponds with theprobable formula wherein w=1 or 2; fz =0 or 1; 2 1 or 2; R denotes amethyl or a carboxyl group; and R signifies a naphthalene nucleus havingthe hydroxyl group attached to one of the positions 1 and 2 and the azogroup attached to the other of said positions.

11. As a new product, a monazo dyestuff which corresponds with theprobable formula wherein x=1 or 2-; R denotes a methyl or a carboxylgroup; and R signifies a naphthalene nucleus having the hydroxyl groupattached to one of the two positions 1 and 2 and the azo group attachedto the other of said positions. I

13. As a new product, a monazo dyestuft' which corresponds with theprobable formula wherein w=1 or 2, and R denotes a methyl or a carboxylgroup.

14. As a new product, a monazo dyestufi' which corresponds with theprobable forwherein a2=0 or 1; 31 1 or 2; R denotes a methyl or acarboxyl group; and R signifies a na hthalene nucleus having thehydroxyl at arched to one of the two positions 1 and 2 and the azo groupattached to the other of said positions.-

15. As a new product, a monazo dyestuff which corresponds with theprobable formula wherein w=1 or 2; R signifies a methyl or a carboxylgroup; and R denotes a naphthalene nucleus having the hydroxyl groupattached to one of the two positions 1 and 2 and the azo group attachedto the'other of said positions.

16. As a new product, a monazo dyestuff which corresponds with theprobable formula QOQI

(HOaS) wherein R denotes a methyl or a carboxyl group.

17. As a new product, the monazo pyrazolone dyestuff which correspondswith the formula 18. As a new product, a monazo dyestutf whichcorresponds With the probable formula wherein 'u=1 or 2; w=0, 1, or2;w==0, 1, or 2; or a carboxyl group.

y=0 or 1; 2:1 or 2; and R denotes a methyl 19. As a new product, amonazo dyestufi which corresponds with the probable formula wherein w=1or 2; 50 0, 1, or 2; g =0, 1, or 2; 2 1 or 2;'and R denotes amethyl or acarboxyl group. 7

20. As a new product, a monazo dyestufl' which corresponds with theprobable formula (Halogen): l

wherein 0 1 or 2; 31 0, 1, or 2; 2 0, 1, or 2; and R denotes a methyl ora carboxylgroup.

21. As a new product, a monazo dyestufl' which corresponds with theprobable for- (HalogenW V wherein 2 1 or 2; y=0, 1, or 2; 2 1 or 2; andRdenotes a methyl or a cerboxyl group.

22. As a new product, a monazo dyestufl which corresponds with theprobable for- (Halogen)y wherein m=1 or 2; z =0, 1 or 2; and R denotes amethyl or a carboxyl group.

23. As a new product, a monazo dyestufi which corresponds with theprobable forwherein 12 1 or 2; y=1 or 2; and R denotes a methyl or acarboxyl group.

2 4.. As a new product, a monazo dyestufi which corresponds with theprobable formula wherein R denotes a methyl or a carboxyl group,

claim 10.

25. As a new product, a monazo dyestulf which corresponds with theprobable formula I-I (N091! /N=CR wherein w=1 or 2; w=0, 1 or 2; y=0 or1; a=1 or 2; and R denotes a methyl or a carboxyl group.

26. As a new product, a monazo dyestull which corresponds with theprobable for mula:

40. Material claim 14.

41. Material claim 15.

42. Material claim 16.

43. Material claim 17.

44. Material claim 18. y

45. Material claim 19.

46. Material claim 20.

47. Material claim 21.

48. Material claim 22.

49. Material claim 23.

50. Material claim. 24.

51. Material claim 25.

52. Material claim 26.

In testimony whereof I aflix my signature.

LEON W. GELLER.

wherein 11 1 or 2; y=0 or 1; 2 1 or 2; and R denotes a methyl or acarboxyl group.

27. Material dyed with a dyestufl claim 1.

28. Material dyed claim 2.

29. Material dyed claim 3.

30. Material dyed claim 4.

31. Material dyed dyed dyed

dyed

dyed

claim 5.

dyed

dyed

dyed

dyed

dyed

dyed

dyed

dyed

dyed

dyed

dyed

dyed dyed with a dyestufi' of with a dyestufi' with a dyestul'f with adyestufi' with a dyestufi with a dyestufi with dyestufi with a dyestutfwith a dyestufi with a dyestufi Material claim 6.

33. Material claim 7.

34. Material claim 8.

35. Material claim 9.

36. Material with a dyestufl with a dyestufi with a dyestutt with adyestufi with a dyestuff with a dyestufif with a dyestufi with adyestufi' with a dyestufi with a dyestufi 37. Material dyestufi claim11.

38. Material claim 12.

89. Material clam 13.

dyed with a with a dyestuff with a dyed dyed

dyestufi dyed with a dyestufl of with a. dyestuflf CERTIFICATE OFCORRECTION.

Patent No. 1,711,639. Granted May 7, 1929, to

I LEON w. GELLER.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,line 108, "(2'- methyl-5'-sulfophenyl)" should be"(2'-methyl-4'-sulfophenyl)"; page 2, line 87, claim 5, in the formulainsert "R"; same page, line 120, claim 7, for the misspelled word"nuclus" read "nucleus"; and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the-Patent Office.

Signed and sealed this 4th day of June, A. D. 1929.

M. J. Moore, (Seal) Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION.

Patent No. 1,711,639.. Grafited t 19299 o LEON W. GELLER.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,line 108, "(2'- methyl-5'-sulf0phenyl)" should be"(2'methyl-4'-sulfophenyl)"; page 2, line 87, claim 5, in the formulainsert "R"; same page, line 120, claim 7, for the misspelled word"nuclus" read "nucleus"; and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Office.

Signed and sealed this 4th day of June, A. D. 1929.

M. J. Moore, (Seal) Acting Commissioner of Patents.

